RU2443715C1 - Solid titanium catalyst component, olefin polymerisation catalyst and olefin polymerisation method - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention discloses a solid titanium catalyst component (I), containing titanium, magnesium, a halogen, a cyclic ester compound (a) and a cyclic ester compound (b); an olefin polymerisation catalyst containing said catalyst component (I); an olefin polymerisation method using said olefin polymerisation catalyst.

EFFECT: disclosed solid titanium catalyst component, olefin polymerisation catalyst and method of obtaining an olefin polymer enable to obtain an olefin polymer having high stereoregularity, wide molecular-weight distribution with high activity; the obtained polymer not only has unique moulding properties, such as the ability for fast drawing and high plasticity during fast drawing, but high hardness with low cost as well.

6 cl, 2 tbl, 1 dwg, 17 ex

Description

Technical field

The invention relates to a solid titanium component of a catalyst, which is mainly used for the polymerization of olefins, preferably for the polymerization of α-olefins. The invention also relates to an olefin polymerization catalyst containing a solid titanium catalyst component. The invention also relates to an olefin polymerization process using an olefin polymerization catalyst.

BACKGROUND OF THE INVENTION

The known catalysts used for the production of olefin polymers, such as ethylene or α-olefin homopolymer and ethylene / α-olefin copolymer containing a titanium compound supported on magnesium halide in the active state (the term "polymerization" hereinafter includes the term " copolymerization ").

As such olefin polymerization catalysts, catalysts containing titanium tetrachloride or titanium trichloride, referred to as Ziegler-Natta catalysts, and catalysts comprising a solid titanium catalyst component consisting of magnesium, titanium, a halogen and an electron donor, and an organometallic compound are widely known.

The latter catalysts are highly active not only in the polymerization of ethylene, but also in the polymerization of α-olefins, such as propylene and 1-butene. In addition, the obtained α-olefin polymers have high stereoregularity.

Japanese Patent Laid-Open Publication No. 6,310 / 1982 (Patent Document 1) reports that among such catalysts, a catalyst using a solid titanium catalyst component in which an electron donor selected from carboxylic acid esters (e.g., phthalic acid ester), is supported, an aluminum alkyl compound as a cocatalyst, and a silicon compound having at least one Si — OR group (where R represents a hydrocarbon group) exhibits exceptional polymerization activity and stereospecificity.

Polymers obtained using the above catalysts often have a narrow molecular weight distribution compared to polymers prepared using a Ziegler-Natta catalyst. It is known that polymers having a narrow molecular weight distribution tend to have "low melt flow", "low melt tension", "low ductility", "low stiffness", etc. On the other hand, in order to increase productivity and reduce prices, various high-speed molding technologies have been developed, such as high-speed drawing techniques, which aim to increase productivity. If such, the above polymers having a narrow molecular weight distribution are designed for high-speed drawing, then narrowing and shattering of the film due to insufficient melt tension become noticeable, which reduces productivity. Therefore, polymers having a high melt tension are required on the market.

To solve this problem, a large number of methods have been developed, for example, to expand the molecular weight distribution of the polymer, a method for producing polymers with different molecular weights by multistage polymerization has been developed (Japanese Patent Application Laid-Open No. 170843/1993 (Patent Document 2), a catalyst containing a plurality of types of electron donors (Japanese Patent Application Laid-Open No. 7703/1991 (Patent Document 3), and a catalyst using an succinic acid ester having an asymmetric carbon in as an electron donor and contained in the solid titanium component of the catalyst (International Publication No. 01/057099 (Patent Document 4), International Publication No. 00/63261 (Patent Document 5), International Publication No. 02/30998 (Patent Document 6)).

Japanese Patent Laid-open No. 114811/2001 (Patent Document 7) and Japanese Patent Laid-open No. 40918/2003 (Patent Document 8), on the other hand, describe a solid component of an olefin (s) polymerization catalyst obtained by contacting a titanium compound, a magnesium compound and an electron donor compound, and an olefin (s) polymerization catalyst containing this catalyst component. In the invention described in patent document 7, an 1,2-cyclohexendicarboxylic acid ester having a trans isomer purity of at least 80% is used as an electron donor compound, and a 1,2-cyclohexendicarboxylic acid diester is used in the invention described in patent document 8 . As an example of such a 1,2-cyclohexendicarboxylic acid diester, only the 1-cyclohexendicarboxylic acid diester is shown, wherein the alkoxycarbonyl group is attached at the first and second positions of the cyclohexene ring of 1-cyclohexene (paragraphs "0021" to "0024" and working examples). However, in patent documents 7 and 8, the molecular weight distribution of the olefin polymer is not indicated.

The applicant in International Publication No. 2006/077945 indicated that a solid titanium catalyst component containing a specific cyclic ester compound as an electron donor component makes it possible to obtain an olefin polymer having an exceptionally broad molecular weight distribution (Patent Document 9).

Patent Document 1: Japanese Patent Application Laid-Open No. 633/1982

Patent Document 2: Japanese Patent Application Laid-Open No. 170843/1993

Patent Document 3: Japanese Patent Application Laid-Open No. 7703/1991

Patent Document 4: International Publication No. 01/057099

Patent Document 5: International Publication No. 00/63261

Patent Document 6: International Publication No. 02/30998

Patent Document 7: Japanese Patent Application Laid-Open No. 114811/2001

Patent Document 8: Japanese Patent Laid-Open No. 40918/2003

Patent Document 9: International Publication No. 2006/077945

Disclosure of invention

The problem solved by the described invention

Studies conducted by the authors of the present invention showed that the catalysts described in patent documents 1 to 8 are not effective enough in terms of expanding the molecular weight distribution of the olefin polymer, or they are catalysts that expand the molecular weight distribution by increasing the weight of the low molecular weight component. On the other hand, a market assessment showed that these catalysts cannot be called satisfactory with respect to improving the melt tension of the obtained olefin polymer, and therefore, from the point of view of reducing the market price, there remains a need to develop a catalyst with which it is possible to obtain an olefin polymer having wide molecular weight distribution.

The cyclic ester compound described in Patent Document 9 contained in the solid titanium catalyst component is more expensive than the electron donors contained in conventional solid titanium catalyst components. For this reason, the solid titanium component of the catalyst described in Patent Document 9 has a high cost and, although it exhibits high efficiency in terms of expanding the molecular weight distribution, it is necessary to reduce its cost.

In accordance with this object of the present invention is a catalyst component and a catalyst with which it is possible to easily and easily obtain an olefin polymer having a wide molecular weight distribution, having high stereospecificity, high melt tension, and suitable for high-speed drawing and high-speed molding and injection molding pressure.

Means for solving this problem

The authors of the present invention conducted serious studies and as a result found that in the case of using a solid titanium catalyst component containing several types of specific cyclic ester compounds having several ester groups of carboxylic acids,

(1) an olefin polymer having a wide molecular weight distribution can be obtained, and

(2) the electron donor acts as a stereoregularity control agent, and an improvement in stereoregularity control can be achieved, which is not observed with a single ester compound. So the authors of the present invention have made a non-existent invention. None of Patent Documents 7 and 8 disclose or suggest a cyclic ester compound (a) represented by the following formula (1) and having a substituent R.

The solid titanium component of catalyst (I) includes titanium, magnesium, halogen, a cyclic ester compound (a) represented by the following formula (1), and a cyclic ester compound (b) represented by the following formula (2).

In the formula (1), n represents an integer from 5 to 10.

R ² and R ³ each independently represents COOR ¹ or R and at least one of R ² and R ³ represents COOR ¹ .

A single bond (with the exception of the bond C ^a -C ^a and the bond C ^a -C ^b in the case where R ³ represents R) in the cyclic skeleton can be replaced by a double bond.

R ¹ each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms.

Among the plurality of Rs, each independently represents an atom or group selected from a hydrogen atom and a hydrocarbon group containing from 1 to 20 carbon atoms, and they can be bonded to each other to form a ring where at least one R cannot be hydrogen.

In the ring structure formed by the binding of several R to each other, a double bond may be present, and when the ring skeleton contains two or more C ^a , each of which is bonded to COOR ¹ , the number of carbon atoms for ring formation is from 5 to 10.

In the formula (2), n represents an integer from 5 to 10.

R ⁴ and R ⁵ each independently represents COOR ¹ or a hydrogen atom, at least one of R ⁴ and R ⁵ represents COOR ¹ , R ¹ each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms, and a single bond (for with the exception of the bond C ^a -C ^a ) in the cyclic skeleton can be replaced by a double bond.

In the formula (1), all bonds between carbon atoms in a cyclic skeleton are predominantly single bonds.

In the formula (1), n is preferably equal to 6.

The cyclic ester compound (a) is advantageously a compound represented by the following formula (1a).

In the formula (1a), n represents an integer from 5 to 10.

A single bond (with the exception of the bond C ^a -C ^a and the bond C ^a -C ^b ) in the cyclic skeleton can be replaced by a double bond.

R ¹ each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms.

Among the plurality of Rs, each independently represents an atom or group selected from a hydrogen atom and a hydrocarbon group containing from 1 to 20 carbon atoms, and they can be bonded to each other to form a ring where at least one R cannot be hydrogen.

In the ring structure formed by the binding of several R to each other, a double bond may be present and when the ring skeleton contains two or more C ^a , each of which is linked to COOR ¹ , the number of carbon atoms for ring formation is from 5 to 10.

In formula (2), all bonds between carbon atoms in a cyclic skeleton are predominantly single bonds.

In the formula (2), n is preferably equal to 6.

The cyclic ester compound (b) is advantageously a compound represented by the following formula (2a).

In the formula (2a), n represents an integer from 5 to 10.

R ¹ each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms. A single bond (with the exception of the bond C ^a -C ^a and the bond C ^a -C ^b ) in the cyclic skeleton can be replaced by a double bond.

The olefin polymerization catalyst of the present invention includes: the above solid titanium catalyst component (I) and an organometallic catalyst component (II) containing a metal selected from groups 1, 2 and 3 of the periodic table.

The olefin polymerization catalyst of the present invention may further include an electron (III) donor.

A method for producing an olefin polymer in accordance with the present invention involves the polymerization of an olefin in the presence of the above olefin polymerization catalyst.

The purpose of the invention

The solid titanium component of the catalyst, the olefin polymerization catalyst, and the method for producing an olefin polymer according to the present invention are suitable for producing an olefin polymer having a broad molecular weight distribution with high activity.

In the case of using a solid titanium catalyst component, an olefin polymerization catalyst and a method for producing an olefin polymer in accordance with the present invention, it is possible to obtain an olefin polymer not only with exceptional molding properties, such as ductility and ductility during high-speed processing, but also rigidity.

The cyclic ester compound (a) is often a more expensive compound than the electron-donor compounds contained in conventional solid titanium catalyst components. On the other hand, the cyclic ester compound (b) is often a compound having a price of not more than 1/10 of the price of the cyclic ester compound (a). In this regard, the solid titanium component of the catalyst of the present invention is capable of providing a wide molecular weight distribution while reducing cost by reducing the content of the cyclic ester compound (a).

Further, in the case of using a solid titanium component of a catalyst containing several types of specific cyclic ester compounds having several ester groups of carboxylic acids, the electron donor acts as an agent controlling the stereoregularity, and it is possible to achieve an improvement in the control of stereoregularity, which is not observed in the case of using a single ester compound .

Brief description of the drawing

Figure 1 is a graph showing the relationship between the ratio of the added DMCHIBU and the value of Mw / Mn.

The best embodiment of the invention

The following is a detailed description of the solid titanium component of catalyst (I), an olefin polymerization catalyst, and a method for producing an olefin polymer in accordance with the present invention.

Solid titanium catalyst component (I)

The solid titanium component of the catalyst (I) of the present invention includes titanium, magnesium, halogen, a cyclic ester compound (a) and a cyclic ester compound (b).

Cyclic ester compound (a)

The cyclic ester compound (a) has several ester groups of carboxylic acids and is represented by the following formula (1)

In the formula (1), n represents an integer from 5 to 10, preferably an integer from 5 to 7, particularly preferably 6.

C ^a and C ^b each represent a carbon atom.

R ² and R ³ each independently represent COOR ¹ or R and at least one of R ² and R ³ represents COOR ¹ .

Although all bonds between the carbon atoms in the cyclic skeleton are predominantly single bonds, any one single bond, other than the C ^a -C ^a bond and the C ^a -C ^b bond in the case where R ³ represents R in the cyclic skeleton, can be replaced by a double communication.

Of the plurality of R ^1, each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms, even more preferably from 4 to 8 carbon atoms, most preferably from 4 up to 6 carbon atoms. Examples of hydrocarbon groups include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group group and eicosyl group. Of these, an n-butyl group, an isobutyl group, a hexyl group and an octyl group are preferred, an n-butyl group and an isobutyl group are more preferred as suitable for the preparation of an olefin polymer having a wide molecular weight distribution.

Among the plurality of R, each independently represents an atom or group selected from a hydrogen atom, a hydrocarbon group containing from 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halide-containing group and a silicon-containing group, but at least one R cannot be hydrogen.

Of the above groups, other than a hydrogen atom, hydrocarbon groups containing from 1 to 20 carbon atoms are preferred. Examples of hydrocarbon groups containing from 1 to 20 carbon atoms include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, vinyl group, phenyl group and octyl group. Of course, aliphatic hydrocarbon groups are preferred and particularly preferred are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. Multiple Rs may be bonded to each other to form a ring, and a double bond may be contained in the ring structure formed by bonding multiple Rs to each other. When the ring skeleton contains two or more C ^a , each of which is associated with COOR ¹ , the number of carbon atoms for the formation of the ring skeleton is from 5 to 10.

Examples of ring structures include the structure of norbornane and the structure of tetracycline dodecene.

Several Rs can be groups containing a carbonyl structure, such as a carboxylic acid ester group, an alkoxy group, a siloxy group, an aldehyde group and an acetyl group, and their substituents preferably contain one or more hydrocarbon groups.

Examples of such cyclic ester compounds (a) include the following, described in International Publication No. 2006/077945 (Patent Document 9), compounds:

diethyl 3-methylcyclohexane-1,2-dicarboxylate,

di-n-propyl 3-methylcyclohexane-1,2-dicarboxylate,

diisopropyl 3-methylcyclohexane-1,2-dicarboxylate,

di-n-butyl 3-methylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-methylcyclohexane-1,2-dicarboxylate,

dihexyl 3-methylcyclohexane-1,2-dicarboxylate,

diheptyl 3-methylcyclohexane-1,2-dicarboxylate,

dioctyl 3-methylcyclohexane-1,2-dicarboxylate,

di-2-ethylhexyl 3-methylcyclohexane-1,2-dicarboxylate,

didecyl 3-methylcyclohexane-1,2-dicarboxylate,

diethyl 4-methylcyclohexane-1,3-dicarboxylate,

diisobutyl 4-methylcyclohexane-1,3-dicarboxylate,

diethyl 4-methylcyclohexane-1,2-dicarboxylate,

di-n-propyl 4-methylcyclohexane-1,2-dicarboxylate,

diisopropyl 4-methylcyclohexane-1,2-dicarboxylate,

di-n-butyl 4-methylcyclohexane-1,2-dicarboxylate,

diisobutyl 4-methylcyclohexane-1,2-dicarboxylate,

dihexyl 4-methylcyclohexane-1,2-dicarboxylate,

diheptyl 4-methylcyclohexane-1,2-dicarboxylate,

dioctyl 4-methylcyclohexane-1,2-dicarboxylate,

di-2-ethylhexyl 4-methylcyclohexane-1,2-dicarboxylate,

didecyl 4-methylcyclohexane-1,2-dicarboxylate,

diethyl 5-methylcyclohexane-1,3-dicarboxylate,

diisobutyl 5-methylcyclohexane-1,3-dicarboxylate,

diethyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

di-n-propyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

diisopropyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

di-n-butyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

diisobutyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

dihexyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

diheptyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

dioctyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

di-2-ethylhexyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

didecyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,

diethyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

di-n-propyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

diisopropyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

di-n-butyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

dihexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

diheptyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

dioctyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

di-2-ethylhexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

didecyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

diethyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

di-n-propyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

diisopropyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

di-n-butyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

diisobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

dihexyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

dioctyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

didecyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

diethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

di-n-propyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

diisopropyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

di-n-butyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

dihexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

diheptyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

dioctyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

di-2-ethylhexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

diethyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

di-n-propyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

diisopropyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

di-n-butyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

dihexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

diheptyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

dioctyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

di-2-ethylhexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

didecyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

diethyl 3-hexylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-hexylcyclohexane-1,2-dicarboxylate,

diethyl 3,6-dihexylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-hexyl-6-pentylcyclohexane-1,2-dicarboxylate,

diethyl 3-methylcyclopentane-1,2-dicarboxylate,

diisobutyl 3-methylcyclopentane-1,2-dicarboxylate,

diheptyl 3-methylcyclocyclopentane-1,2-dicarboxylate,

didecyl 3-methylcyclocyclopentane-1,2-dicarboxylate,

diethyl 4-methylcyclocyclopentane-1,3-dicarboxylate,

diisobutyl 4-methylcyclocyclopentane-1,3-dicarboxylate,

diethyl 4-methylcyclocyclopentane-1,2-dicarboxylate,

diisobutyl 4-methylcyclocyclopentane-1,2-dicarboxylate,

diheptyl 4-methylcyclopentane-1,2-dicarboxylate,

didecyl 4-methylcyclopentane-1,2-dicarboxylate,

diethyl 5-methylcyclopentane-1,3-dicarboxylate,

diisobutyl 5-methylcyclopentane-1,3-dicarboxylate,

diethyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,

diisobutyl 3,4-dimethylcyclopentyl-1,2-dicarboxylate,

diheptyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,

didecyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,

diethyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,

diisobutyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,

diheptyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,

didecyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,

diethyl 3-hexylcyclopentane-1,2-dicarboxylate,

diethyl 3,5-dihexylcyclopentane-1,2-dicarboxylate,

diisobutyl 3-hexyl-5-pentylcyclopentane-1,2-dicarboxylate,

diethyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

di-n-propyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

diisopropyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

di-n-butyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

diisobutyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

dihexyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

dioctyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

didecyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

diethyl 3-methylcycloheptane-1,2-dicarboxylate,

diisobutyl 3-methylcycloheptane-1,2-dicarboxylate,

diheptyl 3-methylcycloheptane-1,2-dicarboxylate,

didecyl 3-methylcycloheptane-1,2-dicarboxylate,

diethyl 4-methylcycloheptane-1,3-dicarboxylate,

diisobutyl 4-methylcycloheptane-1,3-dicarboxylate,

diethyl 4-methylcycloheptane-1,2-dicarboxylate,

diisobutyl 4-methylcycloheptane-1,2-dicarboxylate,

diheptyl 4-methylcycloheptane-1,2-dicarboxylate,

didecyl 4-methylcycloheptane-1,2-dicarboxylate,

diethyl 5-methylcycloheptane-1,3-dicarboxylate,

diisobutyl 5-methylcycloheptane-1,3-dicarboxylate,

diethyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,

diisobutyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,

diheptyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,

didecyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,

diethyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,

diisobutyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,

diheptyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,

didecyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,

diethyl 3-hexylcycloheptane-1,2-dicarboxylate,

diethyl 3,7-dihexylcycloheptane-1,2-dicarboxylate,

diisobutyl 3-hexyl-7-pentylcycloheptane-1,2-dicarboxylate,

diethyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

diisobutyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

di-n-butyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

diisobutyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

dihexyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

dioctyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

didecyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

diethyl 3-methylcyclooctane-1,2-dicarboxylate,

diethyl 3-methylcyclodecane-1,2-dicarboxylate,

diisobutyl 3-vinylcyclohexane-1,2-dicarboxylate,

diisobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,

diethyl 3,6-dicyclohexylcyclohexane-1,2-dicarboxylate,

diisobutyl norbornane-2,3-dicarboxylate,

diisobutyl tetracycline dodecane-2,3-dicarboxylate,

diethyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

di-n-propyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

diisopropyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

di-n-butyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

diisobutyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

dihexyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

diheptyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

dioctyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

di-2-ethylhexyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

didecyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,

diethyl 3,6-dihexyl-4-cyclohexene-1,2-dicarboxylate and

diisobutyl 3-hexyl-6-pentyl-4-cyclohexene-1,2-dicarboxylate.

Further, esters of dicarboxylic acids and cyclic diols corresponding to the above compounds may be mentioned as preferred compounds. Preferred examples of such compounds include:

3,6-dimethylcyclohexyl-1,2-diacetate,

3,6-dimethylcyclohexyl-1,2-dibutanant,

3-methyl-6-propylcyclohexyl-1,2-diol acetate

3-methyl-6-propylcyclohexyl-1,2-butanant,

3,6-dimethylcyclohexyl-1,2-dibenzoate,

3,6-dimethylcyclohexyl-1,2-ditoluate,

3-methyl-6-propylcyclohexyl-1,2-dibenzoate and

3-methyl-6-propylcyclohexyl-1,2-ditoluate.

In such compounds having a diester structure, isomers such as cis and trans isomers formed by several COOR ¹ groups in formula (1) are present, and each structure has an effect that is consistent with the purpose of the present invention. However, compounds with a high trans isomeric form are preferred. In the case of compounds with a high content of the trans-isomeric form, there is a tendency not only to expand the molecular weight distribution, but also the activity and stereoregularity also become higher.

As cyclic ester compounds (a), compounds represented by the following formulas (1-1) to (1-6) are preferred.

In the formulas (1-1) to (1-6), R ¹ and R are the same as described above.

In formulas (1-1) to (1-3), a single bond (with the exception of the bond C ^a -C ^a and the bond C ^a -C ^b ) in the cyclic skeleton can be replaced by a double bond.

In formulas (1-4) to (1-6), a single bond (with the exception of the bond C ^a -C ^a ) in the cyclic skeleton can be replaced by a double bond.

In formulas (1-3) - (1-6), n represents an integer from 7 to 10.

As the cyclic ester compound (a), a compound represented by the following formula (1a) is particularly preferred.

In the formula (1a), n, R ¹ and R are the same as described above (i.e., they have the same meanings as in the formula (1)), and a single bond (except for the bond C ^a -C ^a and the bond C ^a -C ^b ) in the cyclic skeleton may be replaced by a double bond.

Examples of compounds represented by the above formula (1a) include:

diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

di-n-hexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

di-n-hexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

di-n-octyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

di-n-hexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

di-n-octyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

diisobutyl 3,6-diethylcyclohexane-1,2-dicarboxylate,

di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate,

di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate,

diisobutyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,

di-n-hexyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,

di-n-octyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,

diisobutyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,

di-n-hexyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,

di-n-octyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,

di-n-hexyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

di-n-octyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,

diisobutyl 3,5-diethylcyclopentane-1,2-dicarboxylate,

di-n-hexyl 3,5-diethylcyclopentane-1,2-dicarboxylate,

di-n-octyl 3,5-diethylcyclopentane-1,2-dicarboxylate,

diisobutyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,

di-n-hexyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,

di-n-octyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,

diisobutyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,

di-n-hexyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,

di-n-octyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,

di-n-hexyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

di-n-octyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,

diisobutyl 3,7-diethylcycloheptane-1,2-dicarboxylate,

di-n-hexyl 3,7-diethylcycloheptane-1,2-dicarboxylate,

di-n-octyl 3,7-diethylcycloheptane-1,2-dicarboxylate,

diisobutyl 3,7-diethylcycloheptane-1,2-dicarboxylate.

Of the above compounds, more preferred are:

diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

di-n-hexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

di-n-hexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

di-n-octyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,

diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

di-n-hexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

di-n-octyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,

diisobutyl 3,6-diethylcyclohexane-1,2-dicarboxylate,

di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate and

di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate.

Although these compounds can be obtained by the Diels-Alder reaction, polyene compounds used as raw materials are relatively expensive and therefore the cost of the above compounds is slightly higher than the cost of conventional electron-donor compounds.

In such cyclic ester compounds (a) having a diester structure, isomers in the form of cis and trans isomers are present and any structure has an effect that is consistent with the purpose of the present invention. However, compounds with a high trans isomeric form are preferred. In the case of compounds with a high content of the trans-isomeric form, there is a tendency not only to expand the molecular weight distribution of the obtained polymer, but also the activity and stereoregularity of the polymer also become higher. The proportion of the trans form in the total content of cis and trans forms is predominantly at least 51%. Preferably, the lower limit is more than 55%, more preferably 60%, and even more preferably 65%. The upper limit is preferably 100%, more preferably 90%, even more preferably 85% and particularly preferably 79%.

The cyclic ester compound (b)

The cyclic ester compound (b) has several ester groups of carboxylic acids and is represented by the following formula (2)

In the formula (2), n represents an integer from 5 to 10, preferably an integer from 5 to 7, particularly preferably 6.

C ^a and C ^b each represent a carbon atom.

Although all bonds between the carbon atoms in the cyclic skeleton are predominantly single bonds, any one single bond, other than the C ^a -C ^a bond and the C ^a -C ^b bond in the case where R ⁵ represents a hydrogen atom in the cyclic skeleton, can be replaced double bond.

R ⁴ and R ⁵ each independently represent COOR ¹ or a hydrogen atom, at least one of R ⁴ and R ⁵ represents COOR ¹ and R ¹ each independently represents a monovalent hydrocarbon group with 1-20 carbon atoms.

Of the plurality of R ^1, each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms, even more preferably from 4 to 8 carbon atoms, most preferably from 4 up to 6 carbon atoms. Examples of hydrocarbon groups include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group group and eicosyl group. Of these, an n-butyl group, an isobutyl group, a hexyl group and an octyl group are preferred, an n-butyl group and an isobutyl group are more preferred as suitable for the preparation of an olefin polymer having a wide molecular weight distribution.

Examples of such cyclic ester compounds (b) include:

dimethylcyclohexane-1,2-dicarboxylate,

diethyl cyclohexane-1,2-dicarboxylate,

di-n-propyl cyclohexane-1,2-dicarboxylate,

diisopropyl cyclohexane-1,2-dicarboxylate,

di-n-butyl cyclohexane-1,2-dicarboxylate,

diisobutyl cyclohexane-1,2-dicarboxylate,

dihexyl cyclohexane-1,2-dicarboxylate,

diheptyl cyclohexane-1,2-dicarboxylate,

dioctyl cyclohexane-1,2-dicarboxylate,

di-2-ethylhexyl cyclohexane-1,2-dicarboxylate,

didecyl cyclohexane-1,2-dicarboxylate,

diethyl cyclohexane-1,3-dicarboxylate,

diisobutyl cyclohexane-1,3-dicarboxylate,

diethyl cyclopentane-1,2-dicarboxylate,

diisopropyl cyclopentane-1,2-dicarboxylate,

diisobutyl cyclopentane-1,2-dicarboxylate,

diheptyl cyclopentane-1,2-dicarboxylate,

didecyl cyclopentane-1,2-dicarboxylate,

diethyl cyclopentane-1,3-dicarboxylate,

diisobutyl cyclopentane-1,3-dicarboxylate,

diethyl cycloheptane-1,2-dicarboxylate,

diisopropyl cycloheptane-1,2-dicarboxylate,

diisobutyl cycloheptane-1,2-dicarboxylate,

diheptyl cycloheptane-1,2-dicarboxylate,

didecyl cycloheptane-1,2-dicarboxylate,

diethyl cycloheptane-1,3-dicarboxylate,

diisobutyl cycloheptane-1,3-dicarboxylate,

diethyl cyclooctane-1,2-dicarboxylate,

diethyl cyclodecane-1,2-dicarboxylate,

diethyl 4-cyclohexene-1,2-dicarboxylate,

di-n-propyl 4-cyclohexene-1,2-dicarboxylate,

diisopropyl 4-cyclohexene-1,2-dicarboxylate,

di-n-butyl 4-cyclohexene-1,2-dicarboxylate,

diisobutyl 4-cyclohexene-1,2-dicarboxylate,

di-hexyl 4-cyclohexene-1,2-dicarboxylate,

diheptyl 4-cyclohexene-1,2-dicarboxylate,

dioctyl 4-cyclohexene-1,2-dicarboxylate,

didecyl 4-cyclohexene-1,2-dicarboxylate,

diethyl 4-cyclohexene-1,3-dicarboxylate,

diisobutyl 4-cyclohexene-1,3-dicarboxylate,

diethyl 3-cyclopentene-1,2-dicarboxylate,

diisopropyl 3-cyclopentene-1,2-dicarboxylate,

diisobutyl 3-cyclopentene-1,2-dicarboxylate,

diheptyl 3-cyclopentene-1,2-dicarboxylate,

didecyl 3-cyclopentene-1,2-dicarboxylate,

diethyl 3-cyclopentene-1,3-dicarboxylate,

diisobutyl 3-cyclopentene-1,3-dicarboxylate,

diethyl 4-cycloheptene-1,2-dicarboxylate,

diisopropyl 4-cycloheptene-1,2-dicarboxylate,

diisobutyl 4-cycloheptene-1,2-dicarboxylate,

diheptyl 4-cycloheptene-1,2-dicarboxylate,

didecyl 4-cycloheptene-1,2-dicarboxylate,

diethyl 4-cycloheptene-1,3-dicarboxylate,

diisobutyl 4-cycloheptene-1,3-dicarboxylate,

diethyl 5-cyclooctene-1,2-dicarboxylate and

diethyl 6-cyclodecene-1,2-dicarboxylate.

Further, esters of dicarboxylic acids and cyclic diols corresponding to the above compounds may be mentioned as preferred compounds. Examples of such compounds include:

cyclohexyl-1,2-diacetate,

cyclohexyl-1,2-dibutanate,

cyclohexyl-1,2-diabenzoate and

cyclohexyl-1,2-ditoluate.

In such compounds having the above diester structure, isomers in the form of cis and trans isomers are present and any structure has an effect that is consistent with the purpose of the present invention.

The proportion of the trans form in the total content of cis and trans forms is predominantly not less than 51%. Preferably, the lower limit is more than 55%, more preferably 60%, and even more preferably 65%. The upper limit is preferably 100%, more preferably 90%, even more preferably 85% and particularly preferably 79%. Although the reason is not clear, it can be assumed that the variants of the stereoisomers described below fall within the range suitable for expanding the molecular weight distribution.

In particular, the cyclohexane-1,2-dicarboxylic acid diester, where n in formula (2) is 6, has a trans isomer purity within the above ranges.

If the purity of the trans isomer is less than 51%, the effect of the expansion of the molecular weight distribution, activity, stereospecificity, etc. sometimes become unsatisfactory. If the purity of the trans isomer exceeds 79%, the effect of expanding the molecular weight distribution becomes unsatisfactory. In other words, when the purity of the trans isomer is within the above ranges, there are many advantages in terms of expanding the molecular weight distribution of the obtained polymer, the activity of the catalyst, or the high stereo-regularity of the obtained polymer, which are all at a high level.

As cyclic ester compounds (b), compounds having the structure of cycloalkane-1,2-dicarboxylic acid diesters and represented by the following formula (2a) are preferred and are particularly preferred:

di-n-butyl cyclohexane-1,2-dicarboxylate,

diisobutyl cyclohexane-1,2-dicarboxylate,

dihexyl cyclohexane-1,2-dicarboxylate,

diheptyl cyclohexane-1,2-dicarboxylate,

dioctyl cyclohexane-1,2-dicarboxylate,

di-2-ethylhexyl cyclohexane-1,2-dicarboxylate,

diisobutyl cyclopentane-1,2-dicarboxylate,

diheptyl cyclopentane-1,2-dicarboxylate,

diisobutyl cycloheptane-1,2-dicarboxylate,

diheptyl cycloheptane-1,2-dicarboxylate, etc.

In formula (2a), R ¹ , as described above (i.e., R ¹ has the same meanings as in formula (2)), and a single bond (except for the bond C ^a -C ^a and the bond C ^a -C ^b ) in the cyclic skeleton can be replaced by a double bond.

Of the above compounds, more preferred are:

diisobutyl cyclohexane-1,2-dicarboxylate,

dihexyl cyclohexane-1,2-dicarboxylate,

diheptyl cyclohexane-1,2-dicarboxylate,

dioctyl cyclohexane-1,2-dicarboxylate and

di-2-ethylhexyl cyclohexane-1,2-dicarboxylate.

The reason lies not only in their exceptional catalytic properties, but also in the fact that they can be obtained by relatively inexpensive technology using the Diels-Alder reaction.

These compounds may be used alone or as a combination of two or more types. Further, cyclic ester compounds (a) and (b) can be used in combination with the catalyst component described below (c) to the extent not detrimental to the purpose of the present invention.

The combined molar ratio of the cyclic ester compound (a) to the cyclic ester compound (b) (the cyclic ester compound (a) / (the cyclic ester compound (a) + the cyclic ester compound (b)) × 100 (mol%)) is preferably at least 10 mol%. More preferably, the combined molar ratio is at least 30 mol%, even more preferably at least 40 mol%. and particularly preferably at least 50 mol%. The upper limit is preferably 99 mol%, more preferably 90 mol%, even more preferably 85%, and particularly preferably 80 mol%.

The cyclic ester compounds (a) and (b) can be formed during the preparation of the solid titanium component of catalyst (I). For example, by introducing the carboxylic acid anhydrides or halides corresponding to the cyclic ester compounds (a) and (b) into contact with the corresponding alcohols, the cyclic ester compounds (a) and (b) can be incorporated into the solid titanium component of the catalyst.

Using the process for producing an olefin polymer in accordance with the invention, it is possible to obtain a polymer having a wide molecular weight distribution. Although the reason for this is not clear, a suggested explanation is given below.

It is known that cyclic hydrocarbon structures can form various stereomeric structures, such as the shape of a chair and the shape of a bath. In addition, if the cyclic structure has a substituent, then additional variants of the stereo-dimensional structure appear. In addition, if the bond between the carbon atom to which the ester group is attached (COOR ¹ group) and the other carbon atom to which the ester group is attached (COOR ¹ group) is a single bond, and these carbon atoms are between the carbon atoms, forming the cyclic skeleton of the cyclic ester compound, the number of possible variants of the stereomeric structures is expanding. Such variants of the stereomeric structures lead to the formation of various active sites on the solid titanium component of the catalyst (I). As a result, when carrying out the polymerization of an olefin using a solid titanium component of the catalyst (I), olefin polymers with various molecular weights can be obtained immediately. In other words, an olefin polymer having a wide molecular weight distribution can be obtained.

With a wide range of combined molar ratios of the cyclic ester compound (a), that is, even if the content of the cyclic ester compound (a) in the solid titanium component of the catalyst is low, the solid titanium component of the catalyst (I) of the present invention will produce an olefin polymer having an exceptionally broad molecular weight weight distribution. Although the reasons for this are not clear, a hypothetical explanation of this effect follows.

Obviously, due to the presence of the substituent R in the cyclic ester compound (a), an extremely large number of variants of stereomeric structures can form as compared to the ester cyclic compound (b). This suggests that the effect of the cyclic ester compound (a) on the molecular weight distribution becomes dominant, and even if the mixed molar ratio is small, the cyclic ester compound (a) can produce an olefin polymer having an exceptionally wide molecular weight distribution.

On the other hand, the cyclic ester compound (a) and the cyclic ester compound (b) are structurally analogous and therefore, they are unlikely to have a mutual effect on each other, taking into account their basic properties, such as activity and stereoregularity. (If compounds with different structures are used, then activity, stereoregularity or other properties change dramatically or the effect of one compound becomes dominant).

For this reason, even with a low content of cyclic ester compound (a), the solid titanium component of the catalyst (I) of the present invention can produce an olefin polymer having an exceptionally broad molecular weight distribution and high stereoregularity with high activity.

In accordance with the present invention, in the preparation of the solid titanium component of the catalyst (I), a magnesium compound and a titanium compound are used together with the above cyclic ester compounds (a) and (b).

Magnesium compound

Examples of magnesium compounds include well-known compounds, especially

magnesium halides such as magnesium chloride and magnesium bromide;

magnesium alkoxy halides such as magnesium methoxy chloride, magnesium ethoxy chloride and magnesium phenoxy chloride;

magnesium alkoxides such as magnesium ethoxide, magnesium isopropoxide, magnesium butoxide and magnesium 2-ethylhexoxide;

magnesium aryloxides such as phenoxy magnesium; and magnesium salts of carboxylic acids, such as magnesium stearate.

These magnesium compounds can be used alone or as a combination of two or three kinds. Magnesium compounds may be complex compounds or double compounds with other metals or may be in a mixture with compounds of other metals.

Among the above compounds, magnesium compounds containing halide, preferably magnesium halides and especially magnesium chloride, are preferred.

Magnesium alkoxides such as magnesium ethoxide are also preferably used. Magnesium compounds can be derivatives of other compounds, for example, a magnesium compound obtained by contacting an organomagnesium compound such as Grignard reagent with a titanium halide, silicon halide, halogenated alcohol and the like.

Titate mix

A titanium compound is, for example, a tetravalent titanium compound represented by the formula:

Ti (OR) _g X _{4 g} ,

where R represents a hydrocarbon group, X represents a halogen atom and g represents the number 0≤g≥4.

As preferred may be indicated:

tetrahalide titanium such as TiCl ₄ , TiBr ₄ ;

alkoxy titanium trihalides such as Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ and Ti (O-isoC ₄ H ₉ ) Br;

alkoxy titanium dihalides such as Ti (OCH ₃ ) ₂ Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Cl ₂ ;

alkoxy titanium monohalogenides such as Ti (OCH ₃ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl and Ti (OS ₂ H ₅ ) ₃ Br; and

tetraalkoxy titanium such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, tetrahalogen titanium is preferred, particularly preferably titanium tetrachloride. These titanium compounds can be used alone or as a combination of two or three kinds.

Compounds described in detail, for example, in patent document 1 and patent document 2, are also used as such magnesium compounds and titanium compounds mentioned above.

To obtain the solid titanium component of catalyst (I) of the present invention, well-known processes can be used without any limitation, with the exception of the cyclic ester compounds (a) and (b) used. Preferred examples of these processes include the following processes (P-1) to (P-4).

(P-1) A process where a solid adduct consisting of a magnesium compound and a catalyst component (c), cyclic ester compounds (a) and (b) and a titanium compound in a liquid state are brought into contact with each other in suspension in the presence of an inert hydrocarbon solvent.

(P-2) A process where a solid adduct consisting of a magnesium compound and a catalyst component (c), cyclic ester compounds (a) and (b) and a titanium compound in a liquid state are repeatedly brought into contact with each other.

(P-3) A process where a solid adduct consisting of a magnesium compound and a catalyst component (c), cyclic ester compounds (a) and (b) and a titanium compound in a liquid state are repeatedly contacted with each other in suspension in the presence of inert hydrocarbon solvent.

(P-4) A process where a magnesium compound in the form of a liquid consisting of a magnesium compound and a catalyst component (c), a liquid titanium compound and the cyclic ester compounds (a) and (b) are brought into contact with each other.

The reaction temperature upon receipt of the solid titanium component of the catalyst (I) is preferably in the range from −30 ° C. to 150 ° C., more preferably from −25 ° C. to 130 ° C., even more preferably from −25 ° C. to 120 ° C.

The preparation of a solid titanium catalyst component can be carried out in the presence of, if necessary, widely known media. Examples of such media include low polarity aromatic hydrocarbons such as toluene, and well-known aliphatic and alicyclic hydrocarbons such as heptane, octane, decane and cyclohexane. Among them, aliphatic hydrocarbons are preferred.

When carrying out the polymerization reaction of olefins using the solid titanium component of the catalyst (I) obtained under the above conditions, the effect of obtaining a polymer with a high molecular weight distribution is compatible with high catalytic activity and high stereoregularity of the obtained polymer.

Catalytic component (s)

As a catalyst component (c) used to form a solid adduct or a magnesium compound in a liquid state, well-known compounds capable of solubilizing the aforementioned manganese compound at room temperature to 100 ° C, for example, alcohol, aldehyde, amine, carboxylic acid, are preferred and mixtures thereof. Compounds described in patent document 1 and patent document 2 can also be used as such compounds.

Examples of alcohols capable of solubilizing a magnesium compound include:

aliphatic alcohols such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol and dodecanol;

alicyclic alcohols such as benzyl alcohol and methylbenzyl alcohol; and

aliphatic alcohols having an alkoxy group, such as n-butyl cellosolve.

Examples of carboxylic acids include organic carboxylic acids having 7 or more carbon atoms, such as caprylic acid and 2-ethyl caproic acid. Examples of aldehydes include aldehydes having 7 or more carbon atoms, such as capric aldehyde and 2-ethylhexyl aldehyde.

Examples of amines include amines having 6 or more carbon atoms, such as heptylamine, octylamine, nonylamine, laurylamine and 2-ethylhexylamine.

As the catalyst component (c), the above alcohols are preferred, and ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol, etc. are particularly preferred.

Although the amounts of the magnesium compound and the catalyst component (c) used to prepare the solid adduct or magnesium compound in the liquid state strongly depend on their type, contact conditions, etc., the magnesium compounds are used in an amount of from 0.1 to 20 mol / liter, mainly from 0.5 to 5 mol / liter, per unit volume of the catalytic component (s). Also, if necessary, acceptable is used in combination inert with respect to the solid catalyst (c) medium. Preferred examples of such media include well-known hydrocarbon compounds such as heptane, octane and decane.

The component ratio between magnesium in the obtained solid adduct or solid magnesium compound and catalyst component (c) varies depending on the compounds used and cannot be determined without regard to the type of components used, but the amount of catalyst component (c) is preferably not less than 2.0 mol, more preferably not less than 2.2 mol, even more preferably not less than 2.3 mol and particularly preferably not less than 2.4 mol, but not more than 5 mol, per 1 mol of magnesium in the magnesium compound.

Such cyclic ester compounds (a) and (b) and the aforementioned catalytic component (c) can be considered as a component belonging to components that are known by those skilled in the art as electron donor components. It is known that the electron donor component increases the stereoregularity of the obtained polymer, controls the compositional distribution of the obtained polymer, is a coagulant that controls the shape and diameter of the catalyst particles, etc., while maintaining high catalyst activity.

There is reason to believe that the cyclic ester compound (a), in addition, controls the molecular weight distribution, since the cyclic ester compound (a) is itself an electron donor.

In the solid titanium component of the catalyst (I) of the present invention, the halogen / titanium atomic ratio (i.e., the number of moles of halogen atoms / number of moles of titanium atoms) should be from 2 to 100, preferably from 4 to 90;

the molar ratio of the cyclic ester compound (a) / titanium (i.e. the number of moles of the cyclic ester compound (a) / the number of moles of titanium atoms) and the molar ratio of the cyclic ester compound (b) / titanium atom (i.e. the number of moles of the cyclic ester compound (b) / number of moles of titanium atoms) each should be from 0.01 to 100, preferably from 0.2 to 10; and

the molar ratio of the catalytic component (c) / titanium atom should be from 0 to 100, preferably from 0 to 10.

Regarding the preferred ratio of the cyclic ester compound (a) to the cyclic ester compound (b) the lower limit (mol%) of 100 × cyclic ester compound (a) / (cyclic ester compound (a) + cyclic ester compound (b)) is 10 % mol., preferably 30 mol%, more preferably 40 mol%. and particularly preferably 50 mol%, the upper limit is 99 mol%, preferably 90 mol%, more preferably 85 mol%, particularly preferably 80 mol%.

The atomic ratio of magnesium / titanium (i.e., the number of moles of magnesium atoms / number of moles of titanium atoms) should be in the range from 2 to 100, preferably from 4 to 50.

The content of the component, which may be contained in addition to the cyclic ester compounds (a) and (b), for example, the catalytic component (c), is preferably not more than 20% by weight, more preferably not more than 10% by weight, per 100% by weight . cyclic ester compounds (a) and (b).

The conditions for the preparation of the solid titanium component of the catalyst (I) are described in more detail, for example, in EP 585869 A1 (European Patent Kokai No. 0585869) and Patent Document 2, except for the use of cyclic ester compounds (a) and (b).

Olefin Polymerization Catalyst

The olefin polymerization catalyst of the present invention includes: the above solid titanium component of the catalyst (I) of the present invention and

an organometallic component of catalyst (II) containing a metal selected from groups 1, 2 and 3 of the periodic table.

The organometallic component of the catalyst (II)

As the organometallic component of catalyst (II), a compound containing a metal of group 3 of the periodic table can be used, such as an organoaluminum compound, an alkyl complex compound of metal of group 1 of the periodic table and aluminum, or an organometallic compound of metal of group 2 of the periodic table. Of these compounds, an organoaluminum compound is preferred.

Preferred examples of the organometallic catalyst component (II) include organometallic catalyst components known from the literature, such as those described in EP 585869 A1 described above.

Electron donor

The olefin polymerization catalyst of the present invention may contain the previously described electron (III) donor together, if necessary, with an organometallic component of the catalyst (II). The electron (III) donor is mainly an organosilicon compound. An organosilicon compound is, for example, a compound represented by the following formula

where R and R 'each represents a hydrocarbon group and n represents an integer 0 <n <4.

Examples of the silane compounds represented by formula (3), which can be used in the present invention, include diisopropyldimethoxysilane, t-butilmetildimetoksisilan, tert-butilmetildietoksisilan, tert-amilmetildietoksisilan, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, tsiklogeksilmetildietoksisilan, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cycle pentiltrietoksisilan, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane and tsiklopentildimetiletoksisilan.

Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyl dimethoxysilane, cyclohexylmethyldimethoxysilane and dicyclopentyldimethoxysilane are preferred.

Silanes represented by the following formula (4), which are described in International Publication 2004/016662, are also preferred examples of organosilicon compounds.

In the formula (4), R ^a represents a hydrocarbon group containing from 1 to 6 carbon atoms. As R ^a , unsaturated or saturated aliphatic hydrocarbon groups containing from 1 to 6 carbon atoms, or similar groups, and hydrocarbon groups with 2-6 carbon atoms are particularly preferred. Examples of such hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group and a cyclohexyl group. Of these, an ethyl group is particularly preferred.

In the formula (4), R ^b represents a hydrocarbon group containing from 1 to 12 carbon atoms, or hydrogen. As R ^b , unsaturated or saturated aliphatic hydrocarbon groups containing from 1 to 12 carbon atoms, hydrogen or the like can be mentioned. Examples of R ^b include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group , a cyclohexyl group and an octyl group. Of these, an ethyl group is particularly preferred.

In the formula (4), R ^c represents a hydrocarbon group containing from 1 to 12 carbon atoms, or hydrogen. As R ^c , unsaturated or saturated aliphatic hydrocarbon groups containing from 1 to 12 carbon atoms, hydrogen or the like can be mentioned. Examples of such hydrocarbon groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group and an octyl group. Of these, an ethyl group is particularly preferred.

Examples of compounds represented by formula (4) include:

dimethylaminotriethoxysilane,

diethylaminotriethoxysilane,

diethylaminotrimethoxysilane,

diethylaminotri-n-propoxysilane,

di-n-propylaminotriethoxysilane,

methyl n-propylaminotriethoxysilane,

tert-butylaminotriethoxysilane,

ethyl n-propylaminotriethoxysilane,

ethyl isopropylaminotriethoxysilane and

methylethylaminotriethoxysilane.

Another example of an organosilicon compound is a compound represented by the following formula (5).

In the formula (5), RN represents a cyclic amino group. The cyclic amino group is, for example, a perhydroquinoline group, a perhydroisoquinoline group, a 1,2,3,4-tetrahydroquinoline group, a 1,2,3,4-tetrahydroisoquinoline group or an octamethyleneimino group.

Examples of compounds represented by formula (5) include:

(perhydroquinolino) triethoxysilane,

(perhydroisoquinolino) triethoxysilane,

(1,2,3,4-tetrahydroquinolino) triethoxysilane,

(1,2,3,4-tetrahydroisoquinolino) triethoxysilane and

octamethyleneiminotriethoxysilane.

These organosilicon compounds can be used as a combination of two or more types.

A preferred example of another compound useful as an electron donor compound (III) is a polyester compound, which is a compound having two or more ester bonds with an aromatic carboxylic acid ester and / or several carbon atoms.

Of these polyester compounds, 1,3-diesters and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3- are preferred dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane are particularly preferred.

These compounds may be used singly or in combination of two or more types.

If necessary, the olefin polymerization catalyst of the present invention may further comprise other components useful for the polymerization of olefins in addition to the above components. Examples of other components include a carrier such as silicon, an antistatic agent, a particle coagulator, and a storage stabilizer.

The method of producing olefin polymer

A method for producing an olefin polymer in accordance with the invention comprises the polymerization of an olefin using the olefin polymerization catalyst of the present invention. The term "polymerization" sometimes includes not only homopolymerization, but also copolymerization, such as random copolymerization or block copolymerization.

In the process for producing the olefin polymer of the present invention, it is possible to carry out polymerization in the presence of a prepolymerized catalyst, which is obtained by prepolymerizing an α-olefin in the presence of an olefin polymerization catalyst of the present invention. This prepolymerization is carried out by prepolymerization of an α-olefin taken in an amount of from 0.1 to 1000 g, preferably from 0.3 to 500 g, more preferably from 1 to 200 g per 1 g of olefin polymerization catalyst.

In the prepolymerization, a catalyst of a higher concentration than the concentration of the catalyst in the polymerization system can be used.

Preferably, the concentration of the solid titanium component of the catalyst (I) during the prepolymerization is in the range from about 0.001 to 200 mmol, preferably from about 0.01 to 50 mmol, particularly preferably from 0.1 to 20 mmol, based on titanium atom per 1 liter of liquid medium.

The amount of the organometallic component of the catalyst (II) during the prepolymerization should only be such that 0.1 to 1000 g, preferably 0.3 to 500 g, of polymer per 1 g of the solid titanium component of the catalyst (I) are formed, and usually in the range of from about 0.1 to 300 mol, preferably from about 0.5 mol to 100 mol, particularly preferably from 1 to 50 mol, per 1 mol of the titanium atom in the solid titanium component of the catalyst (I).

When carrying out prepolymerization, if necessary, the above electron (III) donor can also be used, in which case the electron donor (III) is used in an amount of from 0.1 to 50 mol, preferably from 0.5 to 30 mol, more preferably from 1 to 10 mol, per 1 mol of the titanium atom in the solid titanium component of the catalyst (I).

The prepolymerization can be carried out by adding olefin and catalyst components to an inert hydrocarbon medium under mild conditions.

In this case, examples of an inert hydrocarbon medium include:

aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene;

alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcycloheptane, 4-cyclohexane, 4-cycloheptane and methyl-4-cycloheptane;

aromatic hydrocarbons such as benzene, toluene and xylene;

halogenated hydrocarbons, such as ethylene chloride and chlorobenzene, and mixtures of these hydrocarbons.

Of the above inert hydrocarbon media, aliphatic hydrocarbons are particularly preferred. In the case of using an inert hydrocarbon medium, prepolymerization is preferably carried out periodically.

On the other hand, prepolymerization can be carried out using the olefin itself as a solvent or in the absence of a solvent. In this case, the prepolymerization is preferably carried out continuously.

The olefin used in the prepolymerization may be the same or different from the olefin used in the polymerization described below, and is preferably propylene.

Preferably, the prepolymerization temperature is in the range from about −20 to + 100 ° C., preferably from about −20 to + 80 ° C., more preferably from 0 to + 40 ° C.

The following describes the polymerization process, which is carried out after the above prepolymerization or without prepolymerization.

Examples of olefins used in the polymerization (i.e., those to be polymerized) include 3-20 carbon alpha olefins, especially straight chain olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1 octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosen, and branched chain olefins such as 4-methyl-1-pentene, 3-methyl-1-pentene and 3-methyl-1-butene. Of these, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene are preferred. From the point of view that the properties of a polymer having a wide molecular weight distribution should be such as to be suitable for the manufacture of resins with high stiffness, propylene, 1-butene and 4-methyl-1-pentene are most preferred.

Ethylene, vinyl aromatic compounds such as styrene and allylbenzene, and vinyl alicyclic compounds such as vinylcyclohexane and vinylcycloheptane can also be used with these α-olefins. Further, together with ethylene and α-olefins, compounds having a variety of unsaturated bonds, for example, dienes (conjugated and non-conjugated dienes), such as cyclopentene, cycloheptene, norbornene, teracycododecene, isoprene and butadiene, can be used as a raw material for polymerization. These compounds can be used singly or in combination of two or more types. (The aforementioned ethylene or olefin, which can be used together with an “α-olefin having from 3 to 20 carbon atoms” is hereinafter referred to as “another olefin”).

Of these olefins, ethylene or a vinyl aromatic compound are preferred. Further, other olefins, such as ethylene, can be used in combination, provided that their amount is a small amount, for example, not more than 10% by weight, preferably not more than 5% by weight, in 100% by weight. total olefins.

In the present invention, prepolymerization and polymerization can be carried out by any bulk polymerization methods, liquid phase polymerization, such as solution polymerization or suspension polymerization, and gas phase polymerization.

In the case of suspension polymerization, an inert hydrocarbon, which is used in the above prepolymerization, or an olefin, which is liquid at the reaction temperature, can be used as a solvent.

The amount of the solid titanium component of the catalyst (I) used in the polymerization process to obtain the polymer of the present invention is usually from about 0.0001 to 0.5 mmol, preferably from about 0.005 to 0.1 mmol, based on titanium atom per 1 liter of polymerization volume . The organometallic component of catalyst (II) is typically used in an amount of from about 1 to 2000 mol, preferably from about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerization catalyst component, in the polymerization system. In the case of using an electron (III) donor, its amount is in the range from 0.001 to 50 mol, preferably from 0.01 to 30 mol, particularly preferably from 0.05 to 20 mol, per 1 mol of the organometallic component of catalyst (II).

When carrying out polymerization in the presence of hydrogen, it is possible to control the molecular weight of the obtained polymer and obtain a polymer having a high melt flow rate.

When carrying out the polymerization in accordance with the present invention, the polymerization temperature of the olefin is usually in the range from about 20 to 200 ° C, preferably from about 30 to 100 ° C, more preferably from 50 to 90 ° C. The pressure is usually in the range from atmospheric to 100 kgf / cm ² (9.8 MPa), preferably from about 2 to 50 kgf / cm ² (from 0.20 to 4.9 MPa). In the polymer production process of the present invention, polymerization can be carried out in any batch process, semi-continuous process and continuous process. Further, the polymerization can be carried out in two or more stages under various reaction conditions. When carrying out such multi-stage polymerization, it becomes possible to further expand the molecular weight distribution of the olefin polymer.

The olefin polymer can be obtained in the form of a homopolymer, a random copolymer and a block copolymer.

When carrying out the polymerization of an olefin, especially during the polymerization of propylene, using a catalyst as described above for the polymerization of olefins, it is possible to obtain a polymer based on propylene with high stereoregularity having a content of insoluble in the decane component of at least 70%, preferably at least 85%, particularly preferably not less than 90%.

In accordance with the method for producing the olefin polymer of the present invention, hereinafter polyolefin, a polyolefin, in particular polypropylene, having a wide molecular weight distribution can be obtained, even if multistage polymerization is not carried out, then polymerization is carried out with fewer stages, for example, by single-stage polymerization. The method for producing an olefin polymer of the present invention is characterized in that an olefin polymer is obtained in which the proportion of the high molecular weight component is higher and the proportion of the low molecular weight component is lower than that of a conventional olefin polymer having an equivalent melt flow rate. These characteristics can be confirmed by the following gel permeation chromatography (GPC) and a polymer with a high Mw / Mn and Mz / Mw value can be obtained.

Polypropylene obtained using a conventional solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor generally has an Mw / Mn of no more than 5 and a Mz / Mw of at least 4 with a melt flow rate (MFR) in the range of 1 up to 10 g / 10 min, where the indicated values of Mw / Mn and Mz / Mw are determined using GPC and are indicators of molecular weight distribution. However, by using the method for producing an olefin polymer of the present invention under the above conditions, an olefin polymer having an Mw / Mn value of from 6 to 30, preferably from 7 to 20. An olefin polymer having an Mz / Mw value of preferably from 4 to 15, more preferably from 4.5 to 10. In accordance with the method for producing the olefin polymer of the present invention, a polymer having a high Mz / Mw value is often obtained. The upper limit of the Mz / Mn value is preferably 300, more preferably 250, particularly preferably 200. In accordance with the method for producing a polypropylene resin, a polymer is often prepared having a high Mz / Mw value and a high Mz / Mn value.

Polypropylene having a high Mw / Mn value has exceptional ductility and rigidity. On the other hand, a high Mz / Mw value indicates that the content of the high molecular weight component is high, and it can be expected that the resulting polypropylene will have a high melt tension and exceptional ductility.

Using the method for producing an olefin polymer of the present invention, a polymer having a wide molecular weight distribution can be obtained even if multi-stage polymerization is not carried out. Therefore, it is possible to simplify the equipment. Using conventional multi-stage polymerization, one can expect to obtain a polymer with excellent ductility and excellent melt tension.

Among other methods for producing polymers having a wide molecular weight distribution, there is a method of dissolving / mixing polymers with different molecular weights and a method of plasticization in melt. However, the polymers obtained by these methods often have poor ductility and melt tension, taking into account the relative complexity of the operations. The reason for this, apparently, is that polymers with different molecular weights are difficult to mix with each other. On the other hand, it is expected that the polymers obtained in accordance with the method for producing olefin polymers of the present invention will have a high melt tension and excellent ductility, since polymers having different molecular weights in an extremely wide range are mixed to a catalytic level, namely, nanoscale .

Further, the method for producing the olefin polymer of the present invention is characterized in that a polymer with controlled stereoregularity is obtained. These characteristics are confirmed by the fact that an olefin polymer is obtained containing a small amount of a decane-soluble component.

Examples

The present invention is further illustrated by the following examples, which do not limit the present invention.

In the following examples, bulk specific gravity, melt flow rate, amount of decane-soluble (insoluble) component, molecular weight distribution, etc. measured using the following methods.

(1) Bulk density (BD)

Bulk density was measured in accordance with JIS K-6721.

(2) Melt Flow Index (MFR)

The melt flow rate (MFR) was determined in accordance with ASTM D1238E at a temperature of 230 ° C.

(3) Amount of decane-soluble (-insoluble) component

Approximately 3 g of propylene polymer is placed in a glass measuring container (weight is measured with an accuracy of 10 ^-4 g, and this value is indicated in the following formulas as “b” (grams)), 500 ml of decane and a small amount of decane-soluble thermal stabilizer , stirred with a stirrer and heated to 150 ° C for 2 hours in a nitrogen atmosphere until the propylene polymer is dissolved. The resulting solution was kept at 150 ° C for 2 hours and then slowly cooled to 23 ° C for 8 hours. The resulting liquid containing a propylene polymer precipitate was filtered under reduced pressure through a standard 25G-4 glass filter manufactured by Iwata Glass Co., Ltd. Then, 100 ml of the filtrate was recovered and dried under vacuum to obtain a batch of decane-soluble component. The weight of the decane-soluble component is measured with an accuracy of 10 ^-4 g and this value is indicated in the following formulas as “a” (gram). The amount of the decane-soluble component is then determined using the following formula.

The content of the decane-soluble component = 100 × (500 × a) / (100b)

The content of the decane-insoluble component = 100-100 × (500 × a) / (100b)

(4) Molecular Weight Distribution

Liquid Chromatograph: ALC / GPC 150-C plus model (differential refractometer with integral type detector) manufactured by Waters Corporation

Column: a pair of GMH6-HT (Tosoh Corporation) and a pair of GMH6-HTL (Tosoh Corporation) connected in series.

Mobile phase: o-dichlorobenzene

Flow rate: 1.0 ml / min

Measurement temperature: 140 ° C

Construction of a calibration curve: standard polystyrene samples were used.

Sample concentration: 0.10% (w / w).

Amount of sample solution: 500 µl.

The measurement was carried out under the above conditions and the obtained chromatogram was analyzed using known methods for calculating the values of Mw / Mn and the value of Mz / Mw. The measurement time for one sample was 60 min.

Example 1

A high speed stirrer having an internal volume of 2 liters (manufactured by Tokushu Kika Kogyo Co., Ltd) was thoroughly purged with nitrogen and then 70 ml of purified decane, 10 g of commercially available magnesium chloride, 24.2 g of ethanol and 3 g of Rheodol SP were placed therein. -S20 (trademark, sorbitan distearate, obtained from Kao Corporation). With stirring, the temperature of the resulting suspension is raised to 120 ° C and stirred at this temperature at a speed of 800 rpm for 30 minutes. Then the suspension is stirred at such a high speed as to avoid the formation of a precipitate, the suspension is transferred to a 2 L glass flask with a stirrer containing 1 L of purified, pre-cooled to -10 ° С decan, using a Teflon tube having an inner diameter of 5 mm. The solid mass formed upon transfer to the liquid is filtered off and washed well with n-heptane to obtain a solid adduct in which 2.8 mol of ethanol is coordinated with 1 mol of magnesium chloride.

A decane suspension of the above solid adduct (23 mmol, calculated as magnesium atom) is fully introduced with stirring in 10 ml of titanium tetrachloride at -20 ° C to obtain a mixed liquid. The mixed liquid is heated to 80 ° C for 5 hours. When the temperature reaches 80 ° C, diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form, DMCHIBU) is added in an amount of 0.14 mol per 1 mol of magnesium atom in a solid adduct and the temperature is raised to 120 ° C. for 40 minutes. When the temperature reaches 120 ° C., diisobutylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) is added in an amount of 0.035 mol per 1 mol of magnesium atom in a solid adduct. The mixture was stirred at 120 ° C. for 90 minutes to complete the reaction.

After 90 minutes, the reaction is complete, the solid part is collected by hot filtration, and this solid part is resuspended in 100 ml of titanium tetrachloride. Then the temperature is increased and, when the temperature reaches 130 ° C, the suspension is stirred at this temperature for 45 minutes to complete the reaction. After 45 minutes, the reaction is complete, the solid is collected by hot filtration and washed well with decane at 100 ° C and heptane until a liberated titanium compound is detected in the wash liquid.

The solid titanium catalyst component (α1) obtained by the above operations is stored in the form of a decane slurry and a portion of the slurry is dried in order to verify the composition of the catalyst.

Polymerization

500 g of propylene and 1 liter of hydrogen are placed in a polymerization apparatus having an internal volume of 2 liters at room temperature, then 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane and 0.004 mmol (in terms of titanium atom) of the solid titanium catalyst component (α1 ) and the inside of the polymerization agent is quickly heated to 70 ° C. After polymerization was carried out at 70 ° C. for 1 hour, the reaction was terminated using a small amount of methanol, and the polymerizator was purged with propylene. The resulting catalyst particles were dried under vacuum overnight at 80 ° C.

The activity of the catalyst, MFR, the amount of decane-insoluble component, bulk specific gravity and molecular weight distribution (Mw / Mn, Mz / Mw) of the obtained polymer are presented in Table 1.

Example 2

Preparation of solid titanium catalyst component (α2)

The solid titanium component of the catalyst (α2) was obtained in the same manner as described in Example 1, except that 0.13 mol of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) was added and 0, 04 mol of diisobutylcyclohexane-1,2-dicarboxylate (mixture of cis and trans form).

Polymerization

The polymerization of propylene is carried out in the same way as described in Example 1, except that instead of the solid titanium catalyst component (α1), a solid titanium catalyst component (α2) is used. The results are presented in Table 1.

Example 3

Preparation of solid titanium catalyst component (α3)

The solid titanium component of the catalyst (α3) was obtained in the same manner as described in Example 1, except that 0.12 mol of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) was added and 0, 06 mol of diisobutylcyclohexane-1,2-dicarboxylate (mixture of cis and trans form).

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 1, except that a solid titanium catalyst component (α3) is used. The results are presented in Table 1.

Example 4

Preparation of solid titanium catalyst component (α4)

The solid titanium component of the catalyst (α4) was obtained in the same manner as described in Example 1, except that 0.09 mol of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) and 0, 09 mol of diisobutylcyclohexane-1,2-dicarboxylate (mixture of cis and trans form).

Polymerization

The polymerization of propylene is carried out in the same way as described in Example 1, except that a solid titanium catalyst component (α4) is used. The results are presented in Table 1.

Comparative Example 1

Synthesis of Solid Titanium Catalyst Component (β1)

The solid titanium component of the catalyst (β1) was obtained in the same manner as described in Example 1, except that 0.175 mol of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) and diisobutylcyclohexane-1 was added. 2-dicarboxylate (mixture of cis and trans form).

Polymerization

The polymerization of propylene is carried out in the same way as described in Example 1, except that the solid titanium catalyst component (β1) is used. The results are presented in Table 1.

Reference Example 2

Synthesis of Solid Titanium Catalyst Component (β2)

A solid titanium catalyst component (β2) was obtained in the same manner as described in Example 1, except that 0.175 mol of diisobutylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) was added at 80 ° C instead of diisobutyl 3,6- dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form), and diisobutylcyclohexane-1,2-dicarboxylate is not added at 120 ° C.

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 1, except that a solid titanium catalyst component (β2) is used. The results are presented in Table 1.

Reference Example 3

Synthesis of Solid Titanium Catalyst Component (β3)

The solid titanium component of the catalyst (β3) was obtained in the same manner as described in Example 1, except that 0.13 mol of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) was added, and instead diisobutylcyclohexane-1,2-dicarboxylate (mixture of cis and trans form) add 0.04 mol of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane.

Polymerization

The polymerization of propylene is carried out in the same way as described in Example 1, except that the solid titanium catalyst component (β3) is used. The results are presented in Table 1.

Reference Example 4

Synthesis of Solid Titanium Catalyst Component (β4)

The solid titanium component of the catalyst (β3) was obtained in the same manner as described in Example 1, except that 0.12 mol of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) was added, and instead diisobutylcyclohexane-1,2-dicarboxylate (mixture of cis and trans form) add 0.06 mol of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane.

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 1, except that a solid titanium catalyst component (β4) is used. The results are presented in Table 1.

Reference Example 5

Synthesis of solid titanium catalyst component β5)

The solid titanium component of the catalyst (β5) was obtained in the same manner as described in Example 1, except that 0.13 mol of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) was added, and instead diisobutylcyclohexane-1,2-dicarboxylate (mixture of cis and trans form) add 0.04 mol of diisobutylphthalate.

Polymerization

The polymerization of propylene is carried out in the same way as described in Example 1, except that a solid titanium catalyst component (β5) is used. The results are presented in Table 1.

Reference Example 6

Synthesis of Solid Titanium Catalyst Component (β6)

The solid titanium component of the catalyst (β6) was obtained in the same manner as described in Example 1, except that instead of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form), 0.15 mol of diisobutylphthalate was added, and diisobutylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) is not added.

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 1, except that a solid titanium catalyst component (β6) is used. The results are presented in Table 1.

Reference Example 7

Synthesis of Solid Titanium Catalyst Component (β7)

The solid titanium component of the catalyst (β7) was obtained in the same manner as described in Example 1, except that instead of diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form), 0.15 mol of 2- isopropyl-2-isobutyl-1,3-dimethoxypropane, and diisobutylcyclohexane-1,2-dicarboxylate (a mixture of cis and trans form) is not added.

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 1, except that a solid titanium catalyst component (β7) is used. The results are presented in Table 1.

Example 5

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 1, except that the solid titanium catalyst component (β4) is used, and dicyclopentyl dimethoxysilane is used instead of cyclohexylmethyldimethoxysilane. The results are presented in Table 2.

Example 6

Preparation of solid titanium catalyst component (α5)

75 g of anhydrous magnesium chloride, 280.3 g of decane and 308.3 g of 2-ethylhexyl alcohol are subjected to a thermal reaction at 130 ° C for 3 hours to obtain a homogeneous solution, then 17.7 g of ethyl benzoate are added to this solution with stirring, and the mixture heated at 130 ° C for 1 hour.

The resulting homogeneous solution was cooled to room temperature and then the entire amount of this homogeneous solution (38 ml) was added dropwise over 45 minutes to 100 ml of titanium tetrachloride at -24 ° C and stirring at a speed of 200 rpm. After the addition is complete, the temperature of the mixed liquid is raised to 80 ° C. over 4.6 hours, and when the temperature reaches 80 ° C., diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (mixture of cis and trans form) is added to the mixed liquid. the amount of 0.0875 mol per atom of Mg. The temperature was raised even higher, and when the temperature reached 120 ° C., diisobutylcyclohexane-1,2-dicarboxylate was added in an amount of 0.0625 mol per amount of atomic Mg. Then the mixture is kept at this temperature for 35 minutes. After completion of the reaction, the solid part was collected by hot filtration and this solid part was resuspended in 100 ml of titanium tetrachloride, followed by repeated thermal reaction at 120 ° C for 35 minutes. After completion of the reaction, the solid was collected by hot filtration and the solid was washed well with decane at 100 ° C and hexane until a liberated titanium compound was detected in the wash liquid. The solid titanium catalyst component (α5) obtained by the above operations is stored as decane sludge and a portion of the sludge is dried in order to verify the composition of the catalyst.

The solid titanium component of the catalyst (α5) has the following composition - 3.0% wt. titanium, 18% wt. magnesium, 8.6% wt. diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, 4.2% wt. diisobutylcyclohexane-1,2-dicarboxylate and 0.6% wt. residual 2-ethylhexyl alcohol.

Polymerization

500 g of propylene and 1 liter of hydrogen are placed in a polymerizer having an internal volume of 2 liters at room temperature, then 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane and 0.004 mmol (in terms of titanium atom) of the solid titanium catalyst component (α5 ) and the inside of the polymerization agent is quickly heated to 70 ° C. After polymerization was carried out at 70 ° C. for 1 hour, the reaction was terminated using a small amount of methanol, and the polymerizator was purged with propylene. The resulting catalyst particles were dried under vacuum overnight at 80 ° C. The activity of the catalyst, MFR, the amount of decane-insoluble component, bulk specific gravity and molecular weight distribution (Mw / Mn, Mz / Mw) of the obtained polymer are presented in Table 2.

Example 7

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 6, except that dicyclopentyl dimethoxysilane is used instead of cyclohexylmethyldimethoxysilane. The results are presented in Table 2.

Reference Example 8

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 1, except that the solid titanium catalyst component (β1) is used and dicyclopentyl dimethoxysilane is used instead of cyclohexylmethyldimethoxysilane. The results are presented in Table 2.

Reference Example 9

Preparation of solid titanium catalyst component (β9)

75 g of anhydrous magnesium chloride, 280.3 g of decane and 308.3 g of 2-ethylhexyl alcohol are subjected to a thermal reaction at 130 ° C for 3 hours to obtain a homogeneous solution, then 17.7 g of ethyl benzoate are added to this solution with stirring, and the mixture heated at 130 ° C for 1 hour.

The resulting homogeneous solution was cooled to room temperature and then the entire amount of this homogeneous solution (38 ml) was added dropwise over 45 minutes to 100 ml of titanium tetrachloride at -24 ° C and stirring at a speed of 200 rpm. After the addition is complete, the temperature of the mixed liquid is raised to 80 ° C. over 4.6 hours, and when the temperature reaches 80 ° C., diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (mixture of cis and trans form) is added to the mixed liquid. the amount of 0.15 mol per atomic Mg. The temperature is raised even higher, and when the temperature reaches 120 ° C, this temperature is maintained for 35 minutes. After completion of the reaction, the solid part was collected by hot filtration and this solid part was resuspended in 100 ml of titanium tetrachloride, followed by repeated thermal reaction at 120 ° C for 35 minutes. After completion of the reaction, the solid was collected by hot filtration and the solid was washed well with decane at 100 ° C and hexane until a liberated titanium compound was detected in the wash liquid. The solid titanium catalyst component (β9) obtained by the above operations is stored as decane sludge and a portion of the sludge is dried in order to verify the composition of the catalyst.

The solid titanium component of the catalyst (β9) has the following composition - 2.8% wt. titanium, 17% wt. magnesium, 11.5% wt. diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate and 0.6% wt. residual 2-ethylhexyl alcohol.

Polymerization

500 g of propylene and 1 liter of hydrogen are placed in a polymerizer having an internal volume of 2 liters at room temperature, then 0.5 mmol of triethylaluminium, 0.1 mmol of cyclohexylmethyldimethoxysilane and 0.004 mmol (in terms of titanium atom) of the solid titanium catalyst component (β9 ) and the inside of the polymerization agent is quickly heated to 70 ° C. After polymerization was carried out at 70 ° C. for 1 hour, the reaction was terminated using a small amount of methanol, and the polymerizator was purged with propylene. The resulting catalyst particles were dried under vacuum overnight at 80 ° C. The activity of the catalyst, MFR, the amount of decane-insoluble component, bulk specific gravity and molecular weight distribution (Mw / Mn, Mz / Mw) of the obtained polymer are presented in Table 2.

Reference Example 10

Polymerization

The polymerization of propylene is carried out in the same manner as described in Example 9, except that the solid titanium catalyst component (β9) is used and dicyclopentyl dimethoxysilane is used instead of cyclohexylmethyldimethoxysilane. The results are presented in Table 2.

Figure 1 shows the relationship between the proportion of added DMCHIBU and the value of Mw / Mn.

Table 1 Electron donor (mol%) Activity Bd Mfr Amount of component insoluble in C10 Mw / mn Mz / mw (but) (b) Phthalate 1,3-diester Kg-PP / g-cat. g / ml g / 10 min The weight.% Project 1 80 twenty - - 34.2 0.46 2,4 98.1 14.6 10.8 Project 2 75 25 - - 35.5 0.49 2.1 98.2 14,4 9.8 Project 3 67 33 - - 36,2 0.49 2,4 98.2 14.0 8.7 Project 4 fifty fifty - - 34.6 0.50 2,3 98.0 14.5 7.5 Comp. Project 1 one hundred 0 - - 32,7 0.48 2.9 98.0 13,4 12.6 Comp. Project 2 0 one hundred - - 25.0 0.47 7.0 96.7 9,4 4,5 Comp. Project 3 75 - - 25 38,0 0.47 3.6 98.7 9.5 7.7 Comp. Project 4 67 - - 33 40.7 0.49 4.4 98.7 9.1 7.2 Comp. Ex.5 75 - 25 - 32,0 0.49 3.3 98.2 11.6 10,2 Comp. Ex.6 0 - one hundred - 32,5 0.49 4.0 98.5 5.8 3.8 Comp. Ex 7 0 - - one hundred 46.6 0.49 8.5 98.5 5.1 3.3 (a): Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (DMCHIBU) (b): Diisobutylcyclohexane-1,2-dicarboxylate Phthalate: Diisobutylphthalate 1,3-Diester: 2-isopropyl-2-isobutyl-1,3-dimethoxypropane

table 2 Solid titanium catalyst component Electron donor Activity Bd Mfr Amount C10 Insoluble Mw / mn Mz / mw Kg-PP / g-cat. g / ml g / 10 min The weight.% Project 4 α4 CMMS 34.6 0.50 2,3 98.0 14.5 7.5 Ex.5 DCPMS 34.0 0.47 1,2 98.0 - Ex.6 α5 CMMS 36.1 0.42 5.8 98.0 14,4 9.3 Ex 7 DCPMS 37.7 0.43 1,5 98.5 14.7 10.6 Comp. pr.1 β1 CMMS 32.7 0.48 2.9 98.0 13,4 12.6 Comp. pr 8 DCPMS 34.3 0.48 3.6 98.1 14.6 13.0 Comp. pr.9 β9 CMMS 23.5 0.42 3.0 97.7 13.9 8.9 Comp. Project 10 DCPMS 31.5 0.44 1,5 97.8 - - CMMS: cyclohexylmethyldimethoxysilane DCPMS: Dicyclopentyldimethoxysilane

Claims (6)

1. The solid titanium component of the catalyst (I), comprising titanium, magnesium, halogen, a cyclic ester compound (a) represented by the following formula (1), and a cyclic ester compound (b) represented by the following formula (2):

where n represents an integer from 5 to 10,
R ² and R ³ each independently represents COOR ¹ or R, and at least one of R ² and R ³ represents COOR ¹ , and a single bond (except for the bond C ^a -C ^a ) in the cyclic skeleton may be replaced by a double bond,
R ¹ each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms,
among the plurality of R, each independently represents an atom or group selected from a hydrogen atom and a hydrocarbon group containing from 1 to 20 carbon atoms, they may be bonded to each other to form a ring where at least one R cannot be hydrogen, and
in the ring structure formed by the binding of several R to each other, a double bond may be contained, and when two or more C ^a , each of which is bonded to COOR ¹ , are contained in the ring skeleton, the number of carbon atoms for ring formation is from 5 to 10;

where n represents an integer from 5 to 10,
R ⁴ and R ⁵ each independently represents COOR ¹ or a hydrogen atom, at least one of R ⁴ and R ⁵ represents COOR ¹ , R ¹ each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms, and a single bond (for with the exception of the bond C ^a -C ^a ) in the cyclic skeleton can be replaced by a double bond. 2. The solid titanium component of the catalyst (I) according to claim 1, where in formulas (1) and (2) all bonds between the carbon atoms of the cyclic skeleton are single bonds. 3. The solid titanium component of the catalyst (I) according to claim 1, where in formulas (1) and (2) n is 6. 4. The solid titanium component of the catalyst (I) according to claim 1, wherein the cyclic ester compound (a) is represented by the following formula (Ia) and the cyclic ester compound (b) is represented by the following formula (2a):

where n represents an integer from 5 to 10,
a single bond (with the exception of the bond C ^a -C ^a and the bond C ^a -C ^b ) in the cyclic skeleton can be replaced by a double bond,
R ¹ each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms,
among the plurality of R, each independently represents an atom or group selected from a hydrogen atom and a hydrocarbon group containing from 1 to 20 carbon atoms, and they may be bonded to each other to form a ring where at least one R cannot be hydrogen, and
in the ring structure formed by the binding of several R to each other, a double bond can be contained, and when two or more C ^a , each of which is linked to COOR ¹ , are contained in the ring skeleton, the number of carbon atoms for ring formation is from 5 to 10;

where n represents an integer from 5 to 10,
R ¹ each independently represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms, and a single bond (with the exception of the C ^a -C ^a bond and the C ^a -C ^b bond) in the cyclic skeleton can be replaced by a double bond. 5. The catalyst for the polymerization of olefins, including:
a solid titanium component of catalyst (I) and an organometallic compound (II) containing a metal atom selected from groups 1, 2 and 3 of the Periodic Table, further comprising an electron (III) donor. 6. The method of polymerization of olefins, including the polymerization of olefin in the presence of an olefin polymerization catalyst according to claim 5.

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